Method of preparing aromatic resins and products thereof

ABSTRACT

Improved lacquer, varnish, and plastic compositions utilizing aromatic polyphenylene polymers having a mean molecular weight of not over 1,000 + OR - 500, reacted with a curing agent, as a polymethylol aromatic compound in the presence of a polymerization catalyst, prepared in solution in a low boiling solvent of about 50* to 120* C.

PTH19 XR;

Smsewza Bilow *June 13, 1972 [54] METHOD OF PREPARING AROMATIC RESINSAND PRODUCTS THEREOF [72] Inventor: Norman Bilow, Los Angeles, Calif,

[73] Assignee: Hughes Aircraft Company, Culver City,

Calif.

The portion of the term of this patent sub- Notice:

sequent to Jan. 12, I988, has been disclaimed.

22 Filed: Jan. 7,- 1971 [21] Appl.No.: 104,818

Related [1.5. Application Data [63] Continuation-impart of Ser. No.665,26l, Sept. 5,

' I967, abandoned.

[52] U.S.CI ..260/47 R, 161/182, 260/2 R,

260/2 H, 260/338 R, 260/49, 260/79, 260/793 M [51] Int. Cl ..C08g 33/00[58] Field ofSearch ..260/2 H,2R, 47 R, 79, 79.3M

[56] References Cited UNITED STATES PATENTS 3,338,844 8/1967 Harris etal. .2 60/2 3,423,335 l/I969 Phillips ..260/2 FOREIGN PATENTS ORAPPLICATIONS 956,334 4/1964 Great Britain OTHER PUBLICATIONS Olah,Friedel-Crafts and-Related Reactions Vol. I Interscience, NY. 1963 (Pp.26- 27, 32'- 33, 201- O3).

Olah, Friedel-Crafts and Related Reactions Vol. II, Interscience, N.YI964 (page 477).

Primary Examiner-Melvin Goldstein Attorney-W, H. MacAlister, Jr. andAlton V. Oberholtzer 57] ABSTRACT 7 Claims, N0 Drawings METHOD OFPREPARING AROMATIC RESINS AND PRODUCTS THEREOF This application is aContinuation-in-Part of Ser. No. 665,261, filed Sept. 5, I967, nowabandoned.

The invention herein described was made in the course of or under acontact with the Air Force.

FIELD OF INVENTION OR IMPROVEMENT This invention relates to animprovement and discovery in the method of preparing aromatic polymerresins providing improved modified and unmodified polyphenylene lacquer,varnish and plastic compositions, and the products thereof. Moreparticularly, the improvement concerns a discovery useful in thepreparation of solutions of aromatic polyphenylene polymers having amean molecular weight critically of not over 1,000 i 500 reacted with acuring agent combination of the character of a polymethylol aromaticcompound and acid catalyst, as 1,4-benzenedimethanol andp-toluenesulfonic acid in a low boiling solvent as chloroform,trichlorethylene, and the like', or mixtures of the same, to effect theproduction of superior coatings, composite laminate structures andmolding parameters in conjunction with facilitating handling to providecomposite structures of improved appearance, structural strength andsuperior hyper-thermal properties for outerspace and commercialapplications, including advantageous usage of the preferred combinationfor mixing with and modifying, or being modified by, the additionthereto of polymers or copolymer resinous forming materials, or mixturesthereof BACKGROUND OF THE INVENTION The preparation of the soluble andplastic poly-phenylenes is provided for in my herewith filed copendingapplication for Process for Preparing Improved Polyphenylene PolymerLacquers and Products," Ser. No. 665,286, filed Sept. 5, 1967, now U.S.Pat. No. 3,560,428, and as generally provided for in the application forMethod of Providing Useful Heat- Setting Aromatic Polymer ResinousCompositions and Products," Ser. No. 665,578 filed Sept. 5, 1967, now USPat. No. 3,555,!08, in which lam co-inventor with Leroy J. Miller,likewise assigned to the present assignee, Hughes Aircraft Company, andincluded herein by reference thereto.

THE INVENTION HEREIN In the above application, we set forth ourdiscovery in these new resinous compositions and their applicability topreparation in soluble and plastic forms in the broad molecular weightrange to l,000 500 to about 5,000 and, more particularly, the extractedpolyphenylenes in the weight range of about 1,000 to about 2,500 inrelatively soluble and curable form. In addition thereto, I have nowdiscovered that solutions of thermosetting polymers of polyphenylene,preferably selected from the group consisting of polymerization productsof biphenyl, orthoand meta-terphenyls, the 2,2'-, 3,3'-, 2,3'-, 2,4'-,3,4-, diphenyl biphenyls, the 1,2,3-, 1,2,4-, and 1,3,5-triphenylbenzenes, mixtures thereof, and mixture thereof with otherphenylene oligomers and polyphenyls with not more than five aromaticrings can be prepared. Less preferably, but, ifdesired, a small amountof benzene up to about one-third by weight may be used with the above.If too much benzene is used, an intractable material is obtained. Thepara monomer is not adaptable to being polymerized alone for producingthe desirable fusible and tractable polyphenylene polymers, but lesspreferably may be present in trace to limited amounts in the monomermixture, or present in a polymer mixture with the above polymerizedmonomers, as a combination mixture, with retention of the desirablepolymers in predominately tractable, fusible and curable form.

The preferred polyphenylenes, including a curing agent therefor, areeasier to handle and produce better and more homogeneous thermosettingpolymer lacquers and plastics when the polyphenylene polymers have amean molecular weight of not over the critical range of 1,000 i 500. Inthis molecular weight range, the polymers are of superior solubility inlow boiling chlorinated solvents such as chloroform, chlorinated benzenesolvents, trichlorethylene and the like, including mixtures thereof,providing in combination with a curing agent improved curablecompositions without the necessity of using different solvents for Astaging to accomplish homogeneity. In addition, the art requires amethod for simplifying the production of improved solutions forpostcuring, or admixture with parapolyphenylene solids and the like orthermoplastic resinous materials which may advantageously be convertedto useful thermoset materials.

It is accordingly an object of this improvement to provide the art withmethods of preparing improved solutions of heat curable polyphenylenelacquer and plastic material and the improved products provided thereby.

Another object of this improvement is to provide the art with animproved method of preparing solutions of the preferred polyphenylenepolymers, with or without modification, and curing agent in a partiallycured state facilitating the method of preparation and application ofthe partially polymerized polyphenylene polymers as thermosetting resinsof resinous curing agents and plastics.

Further objects and advantages will become more clearly apparent andunderstood from the following disclosure or description in conjunctionwith the illustrated example.

The soluble and fusible aromatic polymers that are preferably employedin the process and products of this disclosure are those heretoforeconsidered less desirable because they are less thermally stable priorto cure than higher molecular. weight polymer fractions although theyhave equivalent thermal stability after proper cure and post cure.

As disclosed in the above application, the preferred polymers areobtained by the cationic oxidative polymerization of monomers ofbiphenyl, terphenyl, quaterphenyl, isomers thereof, and mixtures of thesame, and mixtures of the same with phenylene or aromatic monomers andpolymers with not more than S and preferably less than 5 aromatic rings.Otherwise such aromatic polymers are branched polyphenyl resins,polyphenylene oxide resins, polyphenylene sulfide resins, and the like,and mixtures of the same, or mixtures of the preferred polyphenylenepolymers in combination with the curing agent material may be preparedin a usable lacquer or plastic state in condition for thermosetting toprovide useful coating, lamination, and plastic material. As iscontemplated herein, the polyphenyl polymers may be modified with, orutilized to modify polymers and copolymers of phenylene oxide,polyphenylene oxide homopolymers, polyphenylene sulfide homopolymers,polyphenylene sulfide copolymers, and the like polymers, includingaddition thereto of solids of the same and solids ofpara-polyphenylenes, and the like, any of which may be soluble orinsoluble in the solvents such as chloroform,

' trichlorethylene and the halogenated solvents in which thepolyphenylenes are soluble. The solids of para-polyphenylene, and thelike, may be utilized in the manner described in my application for "NewResin Compositions and Method of Preparation" filed herewith, Ser. No.665,284 (now abandoned for C.I.P., Ser. No. 104,779, filed .Ian. 6,l97l, with retention of the prefiled subject pertinent hereto).

The polymers of polyphcnylenes as utilized herein were prepared asfollows, for example:

EXAMPLE A Y A mixture of m-terphenyl (230 g., 1.0 mole), biphenyl (77g., 0.5 mole), benzene (55 g., 0.7 mole), and anhydrous cupric treatingwith 66N then 12N, or either or both, as desired. After drying, theproduct weighs 355 grams. Unreacted monomers and low molecular weightoligomers (-210 grams) were extracted from the crude polymer bycontinuous extracwater; (3) twice with boiling methanol (500 m1. ea.)and washed with. methanol and with water; (4) with boiling concentratedhydrochloric acid (500 ml.) and washed with water; (5) with boilingmethanol (500 ml.) and washed with tion with hot benzene. The lowermolecular weight polymer 5 methanol. The methanol solutions werecombined, and water fraction extracted by the benzene had a meltingpoint ofabout was added to p ecip g- 136mmt y 0f 120 20 C. Continuousextraction of the benzene-insoluble reacted monomer P y Ofa y lowmolecular welEhL residue with hot bromobenzene, at and near itsboilingpoint, The dark, greemsh-brown P y SJ was thoroughly yieldspolymer (69 g.) having a mean molecular weight of 0 dried and extractedwith benzene for l dayinaSoxhlet extracabout 1,500 and melting atl90-220 C. tor. After distilling most of the solvent from the extracts,the product was precipitated with hexane and dried in a vacuum oven at100 1 C. This polymer fraction weighed 15.1 g., EXAMPLE B correspondingto a 29.8 percent yield, and melted at 143 5 158 C. l '11 t' f th e atif hen lene A mixture of 46 g. (0.2 mole) ortho-terphenyl and 30.8 f ?;36 pr PM on o polyp y grams (0.2 mole) biphcnyl and 108 g. 0.8 mole)anhydrous AMP cupric phloride was heated to 135 C. While stirringcontinu- The following e e s mulianeously using in each the ously, 45grams (1.1 mole) anhydrous aluminum chloride same amounts of bi hen l,m-te hen l and on ric chloride. was added in small portions over aone-hour period. Heating Each e p waspconfiucted sy g g mixmre of thenwas f i for hours.at temperamms varying biphcnyl and m-terphenyl to100Cin acommon oil bath, adbetween 158.480 The Inorganic i removed byding the aluminum chloride to the molten monomers, folseveral washingswith N hydrochlonc follows? by lowed by the slow addition, over a periodof about 1% hours at several water washes. This removal may beaccomplished C, of Lhe cupric chlon'de After Lhe cupric Chloride had usmg from. m IZN hydrochloric acld or been added. the reaction mixture ineach case was stirred hydrochloric acid alone, followed by water washes.After exmechanically for three hours at C I tracting the washed productcontinuously in a Soxhlet extrac- A very profound difference inviscosity was "med in each mm a boflmg rmxwre of benzene (5-20 percent?m 0 example after the complete addition of the cupric chloridecyclohexam? for y the F' was extracifid and after the reaction wasessentially complete. At the end of' unuousl) wlth hot chlorobenzenefand near to boiling for the reaction period, the temperature of the oilbath was raised one y- The Chlorobenzene was concentrated to a to 120 Cand the viscosity of each batch was measured with a small Volume and thep y g) was p p ed h Brookfield Viscosimeter. The following Tablesummarizes the cyclohexane. This polymer fraction melted at l80-220 C.results of this series of examples.

Viscosity at 120 Yield, llatch lliphcnyl tit-'lcrphcnyl A1011 (IuCl; incvntipoist's percent 1... 20 1511:.)(013 Ill) gni.)(t).l3 12.3l 5111.((1.10 -5ZH1 plug. ((1. 1 flotllld, i:riitnll )ly lnntcrinl 28 Yieldspecified is the relative yield 01 the polymer fraction which is mostsuitable lacquers. Yitld shown is percent conversion based on (,uClg.Tho yichls represent thi'."iisviiil" for usv in formulatingthcrmosctting polymer polymer fraction as defined by certain solubilitycharacteristics; namely, non-cxtractability with a mixture of boilingbr-nzcnc (10%) in ll(XttIlt. (007 but extractable with a proper solventas hot to boiling chlorohcnzciuor other Slllllllill solvent, :isindicated.

EXAMPLE C 1,3,5-Triphenylbenzene (51.1 g., 0.167 mole) and anhydrouscupric chloride (44.8 g., 0.333 mole) were mixed in a resin kettleheated by means ofan oil bath, and anhydrous aluminum chloride g., 0.34mole) was added in portions over a period of 1% hours. At the start ofthe reaction, the temperature of the reaction mixture was 176 C(triphenylbenzene melts at 170 C). An extremely vigorous reactionoccurred with the addition of the first portion of aluminum chloride (2g.). Copious quantities of gas were evolved, and the mixture foamed upand quickly turned dark. After the initial reaction, the evolution ofhydrogen chloride was very slow and the further addition of aluminumchloride apparently had little effect. The reaction was continued for atotal of 3 hours, with the temperature varying between the limits of 136and 182 C. The mixture remained fluid and was stirred throughout thereaction. When heating ceased, there was essentially no more evolutionof gas.

After cooling, the product was ground in' a mortar and extracted andwashed on the filter as follows: ('1) with concen- EXAMPLE 8'ortho-terphenyl (46.0 g., 0.2 mole) biphcnyl (30.8 g., 0.2 mole) cupricchloride (dry, 108.0 g., 0.8 mole) The above ingredients were mixed andheated to c with stirring.- During the first hour g. (1.1 mole) ofaluminum chloride was added in small portions and the temperature wasallowed to rise to C. Heating continued for 3% hours additional whilethe temperature varied between 158 and C. The hot product was treatedwith dilute hydrochloric acid (6N) several times, then with water. Afterdrying, the polymer was extracted with cyclohexane in a continuousextraction (43 hours) and this procedure removed 30 percent of theproduct (low molecular weight). The remaining portion was then extractedcontinuously with hot toluene. The portion of the polyphenylene whichwas recovered from the third and fourth days extractions melted from 180220 C.

The non-phenolic aromatic polymethylol compounds that are employed inthe present processing are also aromatic structures, having 2 or moremethylol groups, such that the methylol groups are on the same ordifferent fused or attached ring groups. Such compounds have thecharacteristic structures:

formula as HOCH RCH OH and R contains one or more aro matic ring groups,as above illustrated, with two or more methylol groups on the same ordifferent ring structure.

The acid is preferably an aromatic sulfonic acid material asp-toluenesulfonic acid, benzenesulfonic acid, acetamidobenzenesulfonicacid, cyclohexanesulfonic acid'and the like, or other acid material asphosphoric acid, phosphonic or phosphonous acids, alkylphosphonic acids,arylphosphonic acids, alkylphosphonous acids, arylphosphonous acids,sulfuric acid, methane sulfonic acid, and strong halogenated alkylandarylcarboxylic acids, and mixtures of same which can inherently bedesignated R'OH with R the acid moiety minus the OH and which acids oracid like materials are reactive with, the aromatic polymethylolcompound or polyoxyxylylenes and derivatives of such acid materials.Such acid material inherently providing such telomer structure as R'+OCH RCH -l- ,,OR with R the acid moiety as above indicated, R being oneor more aromatic rings, and n is one or more. Such compounds arepreferably used in combination with the polyphenylene polymers to curethe same and compositions thereof. Such combinations, with orwithoutrelative inert or reactive organic or inorganic modifying fillermatter, provide useful insoluble and infusible coatings, laminating andplastic compositions having improved heat resistant or thermal andinsulation properties applicable to ablative conditions and commercialuse.

Illustrative of the combination of the polymethylol and acid catalyst toform the curing agent combination for the herein describe polyphenylenesare the following, for example:

EXAMPLE D 1.5 grams of 1,4-dimethylolbenzene was mixed with 0.1 gram ofp-toluenesulfonic acid monohydrate. The reaction was carried out in anopen beaker to facilitate the removal of water which was evolved duringthe reaction. The mixture was heated to about l20 C to obtain a clearfluid melt an heating was continued at about 100 l20 C with stirring,When the reaction melt had become viscous, heating was stopped and thereaction product cooled. When cool, the product was a plastic white,resinous solid moldable under heat .and pressure or readily soluble inchloroform and other similar solvents with retention of its ability tocure polyphenylene and other aromatic polymers. I

The retention ofthe soluble characteristic is in combination with aretention of available acid in a free or associated state effectingcuring of the aromatic polymers when combined therewith and heat cured.

EXAMPLE E 0.9 gram of l,4-dimethylolbenzene was mixed with 0.6 gram ofp-toluenesulfonic acid monohydrate. The mixture was heated in a beakerup to about 120 C to melt the composition, and the reaction was carriedout for a .period of 40 seconds. The very viscous melt was rapidlycooled to room temperature to give a white solid product which wassoluble in chloroform to yield somewhat cloudy, heat-curable solution.The amount of solvent present determines the fluidity for independentuse, or preferred use as a catalyst system for curing the aromaticcompounds, as described.

EXAMPLE F One hundred and fifty-one grams (L09 mole) of l,4-dimethylolbenzene and 50 grams (0.263 mole) of p-toluenesulfonic acidmonohydrate were dissolved in l,500 ml. of l,l,l-trichloroethane byheating the mixture at its boiling point of 74 C. The mixture was heatedunder reflux with a trap arranged so that water was continuously removedfrom the condensate and just trichloroethane returned to the boilingmixture. The ingredients dissolved as reaction occurred finally to yielda clear solution.

After 2% hours of refluxing, 14 ml. of water had been collected. Afterl0 hours of refluxing, 22 ml. ofwater were found in the trap, and after16 hours when the reaction was terminated, 24 ml. of water had beencollected.

If we assume that 4.7 ml. of water resulted from esterification of thep-toluenesulfonic acid with the dimethylolbenzene, and that anadditional 4.7 ml. of water was obtained from the dehydration of themonohydrate, then l4.6 ml. of water can be assumed to be due to thepolymerization of the dimethylolbenzene. Furthermore, l l/n) moles ofwater will be evolved due to polymerization from each 'mole of 1,4-dimethylolbenzenc, where n is the average degree of polymerization ofthe resulting polymer. ln the case of this example, 1.09 X 18 (l 1/11)is placed equal to 14.6, the water resulting from polymerization.Solving for n, there is obtained n 3.9. This means that approximatelyfour dimethylolbenzene molecules have been joined to give a polymermolecule, which is terminated wholly or in part by ptoluenesulfonategroups.

EXAMPLE G Ten grams of l,3-dimethylolbenzene and 3 grams ofptoluenesulfonic acid in chloroform ml. were heated at reflux for 20hours while continuously removing water, as described. Upon cooling andremoving solvent, the polymerized composition formed a white plasticsolid which was resoluble in hot chloroform.

The above, in solution'form, when added to a refluxing solution of 20grams polyphenylene (MW 1000) in trichloroethylene (40 ml.) and reactedfor 20 hours at 70 C, formed a heat-setting lacquer which was used tocoat, impregnate, and fabricate molded parts, as herein described. Uponcareful evaporation of the solvent, without heat setting of thecomposition, a solid results which can be molded and thermoset, orground for subsequent re-dissolving, dispersion, or molding andthermosetting.

EXAMPLE H A resinous plastic composition and curing agent solution forpolyphenylene oxides, polyphenylene sulfides and polyindene was preparedby refluxing a mixture of l,4-dimethylolbenzene (10 g.),p-toluenesulfonic acid monohydrate (3 g.) and chloroform 100 ml.) forhrs. while removing water azeotropically. The solution may be utilizedas in the above examples or by adding one or more of the abovecomponents thereto and continuing heating under reflux until the mixtureis a homogeneous liquid, to form a coating solution, or upon carefulremoval of the solvent, a solid plastic thermosetting resin results.

EXAMPLE 1 Further, a curing agent solution for the indicated compoundswas prepared by heating at reflux a mixture of 1,3- dimethylolbenzene(10 g), and p-toluenesulfonic acid monohydrate (3g) in chloroform (I00ml.) while removing water continuously. Upon careful removal of thesolvent, a resoluble theremosetting solid resultsv lllustratively, apreferred use is in the resoluble state, as in the above solution form,in combination with a refluxing solution of polyphenylene (20 g., M.W.about 1,000) in trichloroethylene (40 ml.) which, after reacting for 20hours, provides a heat curing lacquer useful in coating, impregnation,and fabricating molded parts. Otherwise, upon careful removal of thesolvent, a thermoplastic solid is obtained capable of being molded andthermoset.

As above illustrated, it is the polymers and telomers ofthe aromaticpolymethylol compounds and the acid catalyst which form the curing agentcombinations which may be illustrated by the structure of the xylyleneglycol condensation polymers A" and B represent the preferred structuresof polyoxyxylylene telomers or polymers. In such representation, nrepresents the extent of polymerization and may be 2 or more. Xrepresents either hydrogen or an acid group where acid group refers tostrong acids with an OH group abstracted, such as the toluenesulfonylgroup, benzenesulfonyl group, acetamidobenzenesulfonyl group,hexanesulfonyl group,

, cyc'lohexanesulfonyl group, other alkyl and aryl sulfinyl and sulfonylgroups, mixtures of the same, and other groups, as herein indicated.Examples of the acids from which such groups are derived aretoluenesulfonic acid, benzenesulfonic acid, acetamidobenzenesulfonicacid, hexanesulfonic acid, cyclohexanesulfonic acid, benzenesulfinicacid, methanesulfonic acid, benzenesulfonyl chloride, phosphoric acid,arylphosphonous acid, sulfuric acid, strong halogenated carboxylicacids, and mixtures of the same. R', R", R', and R" can benon-interfering hydrogen, alkyl, aryl, aralkyl, alkaryl, alkoxy, oraryloxy, and mixtures of the same, including partially halogenatedderivatives thereof. The methylol groups may be on the same or ondifferent and adjacent benzene rings, or on associated benzene ringsconnected by oxygen, sulfur, an alkylene group or an arylene group. Forexample, the non-phenolic polymethylol compounds that are employed toprovide the present illustrative embodiment of starting monomers canhave structures of the following typical character:

which may be generally designated of different structures as follows:

riv mit it wherein the groups R, R", R', and R, may be hydrogen, al"

kyl, aryl, aralkyl, or alkaryl groups. Typical examples of this type ofcompound are p-xylylene glycol ("C" where R, R", R', R hydrogen); mxylylene glycol (D where R', R", R', R hydrogen);l-methyl-2,S-dimethylolbenzene (C where R methyl and R", R', Rhydrogen); l-phenyl- 3,5-dimethylolbenzene (D" where R' 4; phenyl and R,R", R hydrogen); l-phenyl-2-methyl-3,S-dimethylolbenzene (D" where Rphenyl, R" methyl, and R' and R"' hydrogen), and the like, includingmixtures thereof.

In theabove structural formulas, any two adjacent R groups takentogether can represent a single aromatic ring fused to the attachedring. Typical examples of this latter type of compound are:9,l0-dimethylol anthracene (C" where R' and R"= fused phenyl ringand Rand R also fused ring) and the like. Higher methylol derivatives can berepresented by C" and D" and wherein one or more of the R groups is amethylol group and the remainder have hydrogen, alkyl, aryl, alkaryl oraralkyl groups. In a like manner, the R and methylol groups may besituated in a non-interfering relationship, on different and connectedaromatic rings. For the case where theyare situated on differentadjacent rings, we can illustrate by the structural formulas shownbelow:

IlO-(lll1 I'l R" CiizOlI which may be more generally indicated as adifferent structure:

u Rlll 'l cinon RVlllRVll vt v As indicated, comparable monomers andderivatives including othenadditional similar structures can beillustrated, including.those with internal ring closure, of thecharacter disclosed. A typical example of this type of aromaticpolymethylol compound is p,p'-dimethylolbiphenyl (E where R, R", R,'R",R, R, R R"' hydrogen). Furthermore, in the structural formulas, anycombination of two adjacent R groups can represent a fused aromaticring. On the other hand, higher methylol derivatives can be representedby allowing one or more of the R groups of the aromatic polymethylol tobe non-adjacent methylol groups and the remaining R groups to benon-interfering hydrogen, alkyl, aryl, aralkyl, alkaryl, aryloxy, alkoxygroups, including partially halogenated derivatives thereof. Instructure 6" the R" and R" groups are preferably other than hydrogen andcan be alkyl, aryl, aralkyl or alkaryl. Other types of nonphenolicaromatic polymethylol compounds that may be employed in the formation ofthe polymers and telomers of this invention are those compounds in whichthe methylol groups are situated on different benzene rings separatedone from the other by one or more phenylene groups, by aryl and fusedbenzenoid ring groups or by aliphatic groups or chains. All of theillustrated compounds and structures fall under the general descriptionnon-phenolic aromatic polymethylol compounds, including mixtures thereofwhich are applicable herein.

Further examples of the aromatic polymethylol monomeric or polymericmaterials are those similar to the structures in E", "F", G, and H",wherein the rings are joined by a group 2, the compounds having thestructures generally indicated by:

a short chain zilkylenc group or groups and zirylcnc group or groups,and the groups as R', R", R', R, R, R, R', and R as indicated arenon-interfering hydrogen, alkyl, aryl, aralkyl, alkaryl, alkoxy,aryloxy, partially halogenated derivatives thereof and mixtures of thesame which in the presence of a suitable non-metal acid catalyst, canform soluble and plastic aromatic polymers capable of heat setting andcure may be made. The catalyst acid content is usually initially addedin amounts of less than molar equivalent to effect partialpolymerization in this respect, the aromatic polymethylol compound andacid may be added to the aromatic polymers in monomer or telomer form,or both.

A typical and preferred range of the resin forming composition is aningredient proportion of from 2-1 to 4-1 of aromatic phenyl or phenylenepolymers to non-phenolic polymethylol aromatic and acid telomercompound, respectively. The combination may be provided in monomer,polymer, or combination form. It is necessary for those using thecomponents and composition to select the range of properties desired andthen choose those ingredients and reaction conditions which will yieldcompositions having the desired range of properties. For example, whilethe above range is recommended, a range of 10:1 is possible.

To the accomplishment of the foregoing description, further objects andadvantages will be recognized in conjunction with the followingdescription and examples given for purposes of illustration.Accordingly, to the accomplishment of the foregoing and related ends,this invention, discovery, and improvement then comprises the featuresheretofore described and hereinafter illustrated, are inherent herein,and as particularly pointed out in the claims Such illustrativeembodiments are indicative of the various ways in which the principlesof my discovery, invention or improvements may be employed, for example:

EXAMPLE I EXAMPLE 2 Another lacquer solution was prepared as in ExampleI I using 45 g. of polyphenylene polymers l ,000 t 500 m.w.) obtainedfrom the process of preparing same as disclosed in the herewith filedapplication of"Commercially Useful'Polyphcnylene Polymers And Method ofProduction Thereof", Ser. No.

665,262, wherein I am co-inventor with Leroy J. Miller (now abandonedfor C.I.P., Ser. No. 27,178, filed Apr. 4, 1970) the prefiled subject ofwhich; is included herein by reference thereto.

EXAMPLE 3 In another lacquer preparation similar to the process ofExample l, I used 60 of polyphenylene polymers (1,000 :t 500) derived asin Example 2.

EXAMPLE 4 Various solutions of polyphenylenes having a mean molecularweight of 1,000 i 500 were reacted with, a curing agent derived from thereation of an aromatic non-hydroxy polymethylol compound and acidpolymerization catalyst therefor in a solvent solution.

The polyphenylenes were obtained as herein described and in the mannerdisclosed in my herewith filed copending application entitledlmprovement in the Method of Preparing 'Polyphenylene Polymers andProducts Thereof," Ser. No.

665,308, filed Sept. 5, 1967, now US. Pat. No. 3,595,81 l, includedabove and herein by reference thereto, and consising of polymers ofbiphenyl, terphenyl, quaterphenyl isomers of terphenyl and quaterphenyl,mixtures thereof and mixtures of same with other phenyl compounds havingnot more than and preferably less than 5 aromatic rings, in themolecular weight range of 1,0001-500, as indicated.

The curing agent was derived afier the manner of preparation describedin the application of Leroy J. Miller and myself entitled "AromaticResinous Curing System and Method," Serv No. 665,303 (now abandoned forC.l.P. Ser. No. 69,169 filed Sept. 2 l 1970, with retention of theprofiled subject pertinent hereto), and is included herein as describingcuring agents available herein.

Representative of the telomer structure provided by Application SerialNo. 665,303 and the structure R'+OCH RCH -l- ,,OR', wherein R is one ormore aromatic ring groups, n is one or more and R is an acid group ormoiety forming the terminal group minus the'OH as derived from theheretofore indicated acid material.

The reactants can be separately added and applicable in themanner'described in Examples 1 and 2 or in a prepolymerized state, asabove described and as provided in the present example.

Herein, a lacquer preparation, as exemplary, was prepared by mixing 60grams of the soluble polyphenylene polymers (prepared as illustrated)dissolved and slurried in (200 ml.) chloroform with a reaction productof 1,4 xylyleneglycol g.) and p-toluenesulfonic acid monohydrate (5 g.)dissolved in chloroform (75 ml.) and initially reacted by being refluxedfor about -40 hours while removing water azeotropically be fore beingadded to the polyphenylene solution. After mixing, the polyphenylenesolution and the curing agent solution were heated to boiling underreflux for several hours (about 15 to l9). The mixture, then being in apartially reacted state, was cooled and the lacquer formed was used withno further treatment.

Each of the polymer lacquers prepared as in the above Examples were usedto impregnate and coat portions of carbon cloth, known to the trade asHlTCO CCAl. After vacuum drying, typical laminates of several plies werestacked in a mold and molded at 425 F for 2 hours at 3,000 p.s.i. Thesamples were then heated under inert conditions (N for l8 hours at 275 Fand then heat programmed to 550 F over a 108 hour period. After coolingto 200 F, the samples were removed from the oven and the laminates werefully cured, very hard and tough. Each of the laminates prepared fromthe various examples, in a similar manner yielded cured, hard and toughmoldings ofa machinable character.

EXAMPLE 5 A preferred heat curing aromatic polymer solution compositionis preferably prepared as described in Example 1,

from polyphenylene polymers, having a mean molecular weight of 1,000 i500, partially reacted with a polymerized curing agent derived from thereaction of 1,4- benzenedimethanol and p-toluenesulfonic acid in asolvent, as chloroform, trichloroethylene, and the like, or solventmixtures, in-which the polyphenylene polymers, curing agent,

polymerization catalyst and the partially cured polymers are soluble.This polymer composition provides a lacquer of the homogeneousthermosetting partially cured prepolymer which molds at lowertemperature 400" F) and pressures of (500 to 3,000 psi) to producesuperior composites which present a smooth uniform appearance withimproved or greater strength and superior hypcrthermal properties andwhich can withstand temperatures of 400 Cv Additionally, upon carefulevaporation of the solvent, without promoting premature curing oradvancement of the polymer, the remaining solids are redispersablc insuch solvents as mono-,di-, trichlorobcnzcne, tetrachloroethylene,chloroform, trichlorethylene, dioxane, and the like or mixture of suchsolvents. ln solution and dispersed form, the solutions may then beapplied as heat curable coatings and impregnants, as desired. The drypowder can be molded by heat and pressure, to provide fully cured, hardand machinable parts and elements.

Having described the present embodiment of my discovery and improvementin the art, in accordance with the constitutional grant and the PatentStatute, it will be apparent that some modification and variations maybe made within the scope of this disclosure without departing from thespirit and embodiment thereof. The specific embodiments above describedare givenby way of examples illustrative of my invention, discovery andimprovement.

What is claimed is:

l. The method of preparing a homogenous thermosetting polyphenyleneresin composition of selected soluble aromatic polyphenylene polymershaving a mean molecular weight in the critical range of 500 1,500 inpartially reacted copolymerized solvent soluble combination with acuring agent therefor in a ratio of at least 10 to 1, respectively,comprising the steps of:

A. preparing a liquid mixture and'solution of:

l. soluble polyphenylene polymers soluble in a solvent material selectedfrom the group consisting of chloroform, trichloroethylene,monochlorobenzene, dichlorobenzene, trichlorobenzene,tetrachloroethylene, dioxane, or mixtures of such solvents and having amean molecular weight in the range of 500 1,500 and selected from thegroup consisting of the polymer products of biphenyl, terphenyl,quaterphenyl, and isomers thereof, including 2,2-, 3,3'-, 2,3'-, 2,4'-,3,4'-, diphenyl biphenyls, the 1,2,3-, l,2,4-, and l,3,5-triphenylbenzene, including mixtures of said compounds, mixtures of saidcompounds with other phenylene or polyphenyl compounds with not morethan 5 aromatic rings, and including such mixtures with a small amountof benzene up to about onethird by weight, in combination with:

2. a curing agent combination comprised of a coreactant combination of:

a. an aromatic polymethylol or polyoxyxylylene com pound represented bythe formula HOCH RCH OH and having two or more methylol groups on thesame or different ring (R) structure having one or more characteristicrings selected from the group consisting of:

noon:

llOCll:

nocn o oinon (lllytill where X may be including acid material, sulfuricacid, halogenated alkyl or aryl-carboxylic acid material, and mixturesof said acid material characterized as reactive with said aromaticpolymethylol or polyoxyxylylene and derivatives thereof providing curingagents having a relatively generic structure R{-OCH,RCH +,,OR'

wherein R and R are as above defined and n is l or more in combinationwith said soluble polyphenylene polymers,

B. heating said mixture to the reflux temperature of said liquid mixturefor a period of time to obtain a copolymerized homogeneous solution ofsaid soluble polyphenylene polymers and said curing agent, and

C. recovering a solvent soluble lacquer solution of said polymers ofpolyphenylene and curing agent combination soluble in one or more of thesolvents selected from the group consisting of chloroform,trichloroethylene, monochlorobenzene, dichlorobenzene, trichlorobenzene,tetrnchloroethylene, dioxane, or mixtures of such solvents.

2. The method of claim 1 wherein the acid catalyst is a strong acid andthe curing agent is thereby terminated by esterification with saidstrong acid.

3. The method of claim 1 including the step of removing the liquid andretaining the said copolymer mixture in redispersible fusible powderform.

4. The method of claim '1 including the step of heat curing said mixtureto a substantially fully polymerized insoluble solid state.

5. The methodof claim 1 including the steps of applying the saidrecovered copolymer product as an impregnant or coating and heat curingsaid polymers and copolymers to a substantially fully copolymerizedstate.

6. A composite mixture of copolymerized polyphenylene polymers of themolecular weight of about 1,000 to about 2,500 soluble in heatedchlorinated benzene solvents and a curing agent selected from the groupconsistingof an aromatic polymethylol having terminal groups of an acidmoiety minus an OH group, a polyfunctional sulfonyl halide, and mixturesof the same likewise soluble.

7. The product of claim 6 contained in a heat resistant relativelysolvent insoluble state.

2. The method of claim 1 wherein the acid catalyst is a strong acid and the curing agent is thereby terminated by esterification with said strong acid.
 2. a curing agent combination comprised of a coreactant combination of: a. an aromatic polymethylol or polyoxyxylylene compound represented by the formula HOCH2RCH2OH and having two or more methylol groups on the same or different ring (R) structure having one or more characteristic rings selected from the group consisting of:
 3. The method of claim 1 including the step of removing the liquid and retaining the said copolymer mixture in redispersible fusible powder form.
 4. The method of claim 1 including the step of heat curing said mixture to a substantially fully polymerized insoluble solid state.
 5. The method of claim 1 including the steps of applying the said recovered copolymer product as an impregnant or coating and heat curing said polymers and copolymers to a substantially fully copolymerized state.
 6. A composite mixture of copolymerized polyphenylene polymers of the molecular weight of about 1,000 to about 2,500 soluble in heated chlorinated benzene solvents and a curing agent selected from the group consisting of an aromatic polymethylol having terminal groups of an acid moiety minus an OH group, a polyfunctional sulfonyl halide, and mixtures of the same likewise soluble.
 7. The product of claim 6 contained in a heat resistant relatively solvent insoluble state. 